Azo-dyestuffs and process of making same



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Patented Feb. 23, 1932 earner orrics GuiIILAUME DE MONTMOLLIN, HANS enema,

AND JOSEPH SPIELER, OF BASEL,

SWITZERLAND, ASSIG-IJOR-S T SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF

BASEL, swirzrinrnnn BIAKING SAME No Drawing. Application filed June 2?, 1927, Serial No. 201,955, and in Switzerland July 10, 1926.

The present invention relates to the manu facture of new azo-dyestuffs, It comprises the process of making these dyestufis, the dyestull's themselves, and the material dyed with the new dyestuffs.

According to this invention new dyestuffs of the general formula.

' wherein the naphthalene nucleus contains at least one sulfo group and no further substituents, and in which y and 2 stand for hydrogen, alkyl or alkoxy, w stands for O or S, and R represents a compound containing at least two aromatic nuclei of the benzene or the wherein the naphthalene nucelus contains at least one sulfo group and no further substituents, and in which 'y and 2 stand for hydrogen, allryl or alkoXy, and the other contains at least one azo-chromophore, whereupon the new products thus obtained are treated with saponifying agents.

The same dyestuffs may also be obtained by replacing the aminoazo-dyestuff of the general formula -Oacidy1 III a by an aminoazo-dyestulf of the general forlained general formulas.

ll yH -on n I N=N.ONH2

I I y H with a product, such as an aminonaphtholor a diamine, which product, after uniting with the dye stuff, can further be transformed, either by diazotizing and coupling, or by coupling with suitable compounds, into azo-dyestuffs.

. It is further possible to obtain metal containing dyestufi' by treating the products of the present invention in a suitable phase of their preparation with agents yielding metals, such as salts, oxides or hydroxides of copper. That is for instance the case if the dyestuffs contain the residues of the salicylic acid or ifthey have been prepared by means of dia-zotized ortho-aminophenols or diazotized ortho-aminocarboxylic acid.

The new dyestuffs are dark powders which dissolve in water to orange, red, brown and violet solutions. They dye, without a mordant, vegetable fibre orange, red, brown and violet tints which can equalize well, are very fast to light, and can be discharged.

The following examples illustrate the invention, the parts being by weight salting out. It corresponds to the following formula:

Example 1 There is made in known manner a monoazo-dyestuif by diazotizing 23.7 parts of paratoluenesulfonic acid ester of 1 S-aminonaphthol-3 G-disulfonic acid and coupling the diam-compound with 6.9 parts of cresidine; the dyestufi' is dissolved in 300 parts of water. the solution is made alkaline with sodium carbonate and phosgene is passed through it until no free aminoaZo-dyestufi can be detected. The urea thus formed is separated by salting out and filtration. The para-toluenesulfonic acid residue is split off by a short heating at 90 C. in the presence of a solution of sodium hydroxide of 5 per cent. strength. On cooling, the new dycstuif crystallizes. After filtering and drying there is obtained a red-brown powder, which dissolves in water to a bluish-red solution. By treating with reducing agents such as stannous chloride and hydrochloric acid, there are obtained 1 8-aminonaphthol-3 G-disulfonic acid and the i: T diamino-FZ: 2-diinethoxy-5 5dimethyldiphenylurea. It dyes cotton without a mordant very equal bluered tints of excellent fast-ness to light. The

Other products also dyeing red are obtained when there are substituted for the 1 8- a-n'iinonaphthol-ii:fi-disulfonic acid other 1:8-aminonaphthols, for instance 1:8-aminonaphtholi-sulfonic acid and 1:8-aminonaphthol lzG-disulfonic acid. The substitution of other amines, such as ethoxycresidine of the formula or para-xylidine for the cresidine leads also to bluish-red dyeing products, meta-toluidine leads to a more brown-red dyeing product.

Example 2 62.1 parts of the nionoazo-dyestuif made from diazotized para-toluenesulfonic acid ester of 1: -amino-naphthol-ZE:G-disulfonic acid and cresidine are dissolved in 1200 parts of water together with 4-3.8 parts of the saponified' dyestufi froml molecule of diazotized inono-acetyl-para-phenylenediainine-sulfonic acid and 1 molecule of 2:8-aininonaphtholdyeings are easily discharged. It corre- 6-sulfonic acid (coupled in acid solution) sponds to the followlng formula and after addition of 50 parts of calcined N=N NH- 0 O-NH- N=N on 0H3 om no S0 11 door The same product is formed by the action of phosgene on the product made by coupling diazotized 1 8-ai'ninonaphthol3: (S-disulfonic acid with cresidine.

The corresponding dyestuif derived from thiophosgene dyes cotton more bluish tints. It can be prepared as follows 50 parts of the monoazo-dyestuff made from diazotized para-tohienesulfonic acid ester of 1 8a1ninonaphthol-3:G-disulfonic acid and cresidine are introduced into av mixture consisting of parts of caustic potash, 320 parts of alcohol and parts of carbon bisulfide, and are boiled for a long time in an apparatus provided with a reflux condenser. After cool ing the dyestuif is filtered, saponified by a short heating in the presence of a dilute solution of sodium hydroxide, and isolated by sodium carbonate the solution is treated with phosgene until the diazotizability of the mass has practically disappeared. By salting out there is obtained a dyestufi" which dyes cotton red, fast to light. By heating the dyestuff to 7595 C. in presence of caustic soda solution of 3 per cent. strength the toluenesulfonic acid ester group is split off. There is obtained a dyestuff which dyes cotton blucred of pronounced fastness to light. The same dyestuff is produced if for the product of coupling diazotized para-toluenesulfonic acid ester of 1:S-aminonaphthoLS:G-disulfonic acid with cresidine is substituted the product of coupling diazotized 1:8-aminonaphthol-3 G-disulfonic acid with cresidine, whereby splitting off of the para-toluenesulfonic acid residue does not arise. The new dyestufi' corresponds to the" following formula. 7 1

SOIE 0CH3 SOQII SOaH A violet dyeing dyestuii' is obtained by uniting the dyestufl made from 1 8-amino naphthol-3:G-disulfonic acid and c'residine by means of phosgene with the trisazo-dyestuff Which is obtained by coupling diazotized 2 naphthylamine 4 8 disulfonic acid with a-naphthylamine, by further diazotizing and coupling with l-naphthylaminc-6- sulfonic acid and finally by diazotizing once SOSH i: 8-disulfonic acid, a-naphthylan'iine and 1'- naphthylamine-G-sulfonic acid. It corresponds to the following formula:

SO3H OCHs Dyestufi s of this type may also be produced on the fibre. For'instance cotton may be dyed by the intermediate dyestufl' which can be obtained by uniting one molecule of the dye- SOaH HO- SOaH stuff made from 1 8-aminonaphthol-8: G-disulfonic acid and cresidine with one molecule of 2: 5-aminonaphthol-T-sulfonic acid by means of phosgene, and developed by after treatment with diazobenzene or diaz-paranitrobenzene. The dyestuii developed with diazo-para-nitrobenzene corresponds to the formula: i

OOHa

However, by uniting the dyestuli' made from 1 8-amino-naphthol-B (i-disultonic acid and cresidine with one molecule of chloro-mcta-phenylenedia1nine or para or metaphenylenediaininesultonic acid by means of phosgene, dyestuffs are obtained which are further diazotized in substance or on the fibre and coupled with B-naphthol, B-hydroxynaphthoic acid or with the arylides of the ,8-hyd'roxynapthoic acid yielding red to red-brown dyestuii s. For instance the dyes uff made from 1: 8-a1ninonaphthol-3 6-disulfonic acid and cresidine with one molecule of para-phenylenediaminesulfonic acid by means of phosgene, which dyestufl' is further diazotized in substance or on the fibre and coupled with the anilide of the B-hydro- Xynaphthoic acid has the following formula:

SOaH

Example 3 62.1 parts of the monoa-zo-dyestufi from diazotized para-toluenesulfcnic acid ester of $0311 SOQH 1 S-aminonaphtholfi b disultonic acid and cresidine and 25.7 parts of the reduced amdyestufi' from diazotized para-nitraniline and salicylic acid are treated with phosgene in the manner described in the preceding examples and then with alkali. There is obtained before the splitting off of the para-toluenesulfonic acid residue an orange-dyeing dyestufi, and after the splitting off of the said residue an orange-red-dyeing dyestuff fast to light. It corresponds to the following formula:

SOgH OCH;

H OH:

Both these dyestuffs have enhanced fast-ness to light when they are converted into copper compounds.

Further orange-dyeing dyestuffs are obtained by substituting for the reduction product of the dyestuif from diazotized paranitraniline and salicylic acid aminoazobenzene or the product of coupling a diazotized aminosulfonic acid of the benzene or naphthalene series, such as sulfanilic acid, a chloranilinesulfonic acid, a toluidinesulfonic acid, an aminophenolethersulfonic acid, 06- or ,B-napthylamine, or a monoor disulfonic acid thereof, such as 1 et-naphthylaminesulfonic acid, l-naphthylamine-Qztor 3 8- or 4 S-disulfonic acid, 2-11aphthylamine- 8- disulfonic acid etc., with an amine, such as cresidine, Xylidine, ortho-toluidine, metatoluidine, or aniline etc.

Dyestuffs containing copper may be obtained as follows:

One molecule of the dyestuif made from diazotized 1 8 aminonaphthol 3 6 disulfonic acid and cresidine is united with one molecule of the dyestuif obtained from diazotized ortho-aminophenolsulfonic acid of the formula and 2: 5-aminonaphthol-T-sulfonic acid by means of phosgene. The dyestuff thus obtained is treated with copper oxide ammonia or copper sulfate, and the new copper compound is isolated in known manner. It dyes cotton red tints.

Example 4 A dye-bath is prepared with 2 per cent. of the dyestuif described in the first paragraph of Example 1 and 2 per cent. of sodium carbonate; cotton goods are introduced at 60 C. and the bath is heated to boiling; after a quarter of an hour 30 per cent. of Glauber salt are added and the boiling is continued for a further half-an-hour. The cotton is thereby dyed blue-red fast to light.

What we claim is:

1. A process for the manufacture of a20- COOH dyestuffs of the general formula wherein the naphthalene nucleus contains at least one sulfo group and no further substituents, and 2 stand for hydrogen, alkyl or alkoxy, a" stands for O or S, and R represents a compound containing at least two aromatic nuclei of the benzene or naphthalene series united by at least one azo-chromophore, by uniting, by means of compounds of the general formula y '=C=m wherein m stands for O or and y stands for S or C1 two molecular proportions of aminoazo-dyestuffs, of which at least one corresponds to the general formula wherein the naphthalene nucleus contains at least one sulfo group and no further substituents, and a stand for hydrogen, alkyl or alkoxy, and R represents a compound containing at least two aromatic nuclei of the benzene or naphthalene series united by at least one aZo-chromophore, by uniting, by

to I

means of phosgene, two -molecular proportions of aminoazo-dyestuffs, of Which at least one corresponds to the general formula wherein 3 and 2 stand for hydrogen, alkyl or alkoxy, and R represents a compound containing at leastjtwo aromatic nuclei of the benzene or naphthalene series united by atleast one azo-chromophore, by uniting two molecular proportionsof aminoazo-dyestufi's,

SIO H sosrr of which at least one, corresponds to the general' formula H v z I l s osn wherein y and 2 stand for hydrogen, alkyl' or allroxy, and the other contains at least one azo-chromophore, by means .of phosgene, whereupon the new products thus obtained are treat'ed'with saponifying agents.

4. A process for the manufacture of azo dyestuffs of the general formula:

wherein g and a stand for hydrogen, alkyl or alkoxy, and R and R represent aromatic series and the other to the naphthalene series,

by 'dlllt'illg, by means of phosgene, two aminoaZo-dyestuffs, of which one corresponds to the formula SOsH T l l Oacidy1 y H SOaH wherein 7 and 2 stand for h dro en alk l or allroxy, and. the other corresponds to the general formula NH R N=N'R wherein R and R have the above given signifloat-ion, obtained are treated with saponifying agents. 5. A process for the manufacture of a20- dyestuffs corresponding'to the general formula: 7'

SIOJH SOaH wherein 2 stands for hydrogen, alkyl or alkoxy, by uniting, by means of phosgene, two molecular proportions of the dyestuffs corresponding to the 'eneral formula wherein 2 stands for hydrogen, alkyl or.

allroxy, whereupon the new products thus obtained are treated with saponifying agents. 6. A process for the manufacture of an azodyestufi corresponding to the formula lei of which one belongs to the benzene whereupon the new products thus by uniting two molecules of the dyestuff corresponding to the formula SOaH OCHa by means of phosgene, whereupon the new product thus obtained is treated with saponifying agents.

7. As new products the dyestuffs corresponding to the general formula wherein the naphthalene nucleus contains at least one sulfo group and no further substituents, g and .2 stand for hydrogen, alkyl or alkoxy, m stands for O or S, and R represents a compound containing at least two aromatic nuclei of the benzene or naphthalene series united by at least one azo-chromophore, which products form dark powders which dissolve in water to orange, red, brown and violet solutions, and dye, without a mordant, vegetable fibre orange, red, brown and violet tints which can equalize well, are very fast to light, and can be discharged.

8. As new products the dyestuffs of the general formula wherein the naphthalene nucleus contains at least one sulfo group and no further substituents, y and 2 stand for hydrogen, alkyl or alkoxy, and R represents a compound containing at least two aromatic nuclei of the benzene or naphthalene series united by at least one azochromophore, which products form dark powders which dissolve in water to orange, red, brown and violet solutions, and dye, without a mordant, vegetable fibre orange, red, brown and violet tints which can equalize well, are very fast to light, and can be discharged.

9. As new products the dyestuffs 0f the general formula OII H z v wherin the naphthalene nucleus contains two sulfo groups and no further substituents, 3 and 2 stand for hydrogen, alkyl or alkoxy, and R represents a compound containing at least two aromatic nuclei of the benzene or naphthalene series united by at least one amchromophore, which products form dark powders which dissolve in water to orange, red, brown and violet solutions, and dye, without a mordant, vegetable fibre orange, red, brown and violet tints which can equalize well, are very fast to light, and can be discharged.

10. As new products the dyestuffs of the general formula wherein y and 2 stand for hydrogen, alkyl or alkoxy, and R represents a compound containing at least two aromatic nuclei of the benzene or naphthalene series united by at least one azo-chromophore, which products form dark powders which dissolve in water to orange, red, brown and violet solutions, and dye, without a mordant, vegetable fibre orange, red, brown and violet tints which can equalize well, are very fast to light and can be discharged.

11. As new products the dyestuffs of the general formula wherein 3 and 2 stand for hydrogen, alkyl or alkoxy, and R and R represent aromatic nuclei of which one belongs to the benzene series, and the other to the naphthalene series, which products form dark powders which dissolve in water to orange, red and brown solutions, and dye, without a mordant, vegetable fibre orange, red and brown tints which can equalize well, are very fast to light and can be discharged.

12. As new products the dyestuffs of the general formula OH H z 2 H HO- OaE OH: H H H; S OJI wherein 2 stands for hydrogen, alkyl or alkoxy which products form dark powders, dissolving in water to solutions varying from red-brown to bluish-red color, dyeing cotton, without a Inordant, the same tints which are of excellent fastness to light, equalize very well, can be easily discharged, and which products, on being treated with reducing agents, such as stannous chloride and hydrochloric acid, split into 4:4L-dia1ninodiphenylurea compounds and 1:8-aminonaphthol-3 G-disulfonic acid.

' 13. As a new product the dyestuii of the general formula SOzH 00113 01130 NHO ONH CH3 HO which forms a red-brown powder, dissolving in water to a bluish-red solution, dyeing cotton, without a niordant, very equal'bluered tints of excellent fastness to light, which can be easily discharged, and which product, on being treated with reducing agents, such as stannous chloride and hydrochloric acid, splits into the 4 4c-diamin0-2 2-dimethoxy- 5 5-dilnethyldiphenylurea and the 1 8-a1ninonaphthol-3 6-disulfonic acid.

In witness 'Whereof we have hereunto signed our names this 15th day of June, 1927.

GUILLAUME DE MONTMOLLIN.

HANS GUBLER.

JOSEPH SPIELER. 

